Recovery of mixed solvents from mineral oils



Feb. 7., 1939;

E. KOENEMANN El' AL RECOVERY OF MIXED SOLVENTS FROM MINERAL OILS Filed Aug. l6, 1954 2 Sheets-Sheet l khr (lttorneg Feb. 7, 1 939. E. KOENEMANN ET'AL l 2,145,679

RECOVERY OF IIXED SOLVENTS FRC MINERAL OILS Filed Aug. 1s, 1954 2 sheets-sheet 2 NQTLY 50A VAPOR Eiga Z .5oz ac/za ramon Patented Feb. 7,1939

PATENT- oFFicl-zA iRECOVERY F MIXED SOLVENTS FROM IVIINERAL OILS Ernst Koenemann. and Hans Ramser, Berlin, Germany, assignors to Edcleanu Gesellschaft, m. b. H., a German corporation 'y Application August 16, 1934, Serial No. 740,191 In Germany August 26, 1933 2s claims; (ci. 2oz-4s) Our invention relates to a method of recovering mixed-solvents from solutions `thereof with hydrocarbon oils, such as mineral oils. A particular object of the invention is tov provide' for efflcient recovery of the mixed-solvent contained' in the rafnate and extract solutions resulting from the mixed-solvent treatment of mineral 1u- 4bricating oil fractions, with special reference to the? recoveryof the 'components in solvent mixm tures of .liquid-SO2 and benzol or the like, a1-

though the invention is not limited thereto.

The scope and flexibility of the process of rening hydrocarbon oils with liquid-SO: (Ede leanu process) h been increased by the use employed and suggestedfor this purpose are benzol and its homologues, chloroform, ether, carbon disulfide, and mixtures of these substances.'

In recovering such solvent mixtures from the` railinate and extract solutions resulting from the extraction of the raw oil with the mixed-solvent, it is very important -to completely free the ra'lnate andextract from the costly solvent and to recover the latter for repeated use. This may "m be accomplished by evaporation methods employing high temperature, but as most of these solvent mixtures contain a solvent which is detrimental to the oil at high temperatures it is necessary to apply other methods of recovery. A

principalobject of this invention is tov provide such a method and one which is of general ap plication for the eilicient recovery of solventv mixtures.

According to our invention one of the solvents 4" of the mixture is utilized for stripping out the otheryor others, ,from the oil-solvent solutions. It ls not essential which of the solvent componentsis used for stripping. For example in the caseof solvent mixtures comprised of liquid-.SO2

45. and one or more solvent aids, the sulfur-dioxide may be used for strippingA out the solvent aid, or

the solvent aid (or one of the solvent aids in case several are employed) Imay be used as the stripping agent. Since a portion of the solvent used as the stripping agent` will remain in the oil after the stripping step, while the other solvent or solvents Will be completely removed by the stripping, it is generally preferable to use that sol- 55 vent component as the stripping agent which can of an auxiliarysolvent, or solvent aid, mixed with' be'most easily or advantageously removed from the oil following the solvent stripping.

The stripping pressure is determined by the method used for condensing the expelled or, stripped out solvent mixture.- If, for instance, it is desired to recover the solvent mixture as such, without separating the different solvent components, a pressure should preferably be employed which will be high enough to permit all of the components, including that of the highi est vapor pressure, to be condensed-in a watercooled condenser. On the other hand, if' it is desired to separately recover the diierent components of the solvent mixture, it is preferable to strip at a lower pressure in'order to facilitate fractionating the solvents taken overhead in the stripper. I l

If 'the lowest-boiling component of the solvent mixture is used as the stripping agent,.the stripping is preferably performed by blowing this 20 solvent substance, as a gas, through the solution of oil and solvents. In the case of liquid-Soabenzol solvent solutions, this means that SO2 ngas will be used. The residual solvent remaining in the oil, comprising the lowest-boiling component 25 of the solvent mixture, may then be readily removed by the'mere application of heat and/or vacuum suilicient to vapcrize the solvent from the oil. 0r the solvent may be vaporized from the-oil by stripping with steam or other gas from which the solvent can later be recovered.

However, if the highest-boiling solvent component is used for stripping, vthe preferred procedure is to reboil a portion of the oil-solvent solution leaving the stripper and recycle it into the lower part of the stripper, employing a temperature sufilciently high so that all of the solvent content except a small fraction of this highest-boiling component is vaporized. The highest-boiling solvent component will thereby exert a blowing 4o or stripping action on the oil solution entering the stripper, thus removing all of the lower-boiling solvent components.

The removal of the residual amount of the highest-boiling solvent component, which remains in the oil after the stripping `just described, may be effected by subsequently stripping the oil with the aid of steam, or other gas, from which. the stripped-out solventl can later be recovered. In certain cases it will be possible to free the oil of this residual solvent by the mere application of heat and/or vacuum, jwithout steam-stripping, particularly when the solvent is a substance which is chemically indifferent to the oil at elevated temperatures and thus permits the use of the i55A latter without causing decomposition of the oil or the formation of undesirable reaction products.

The amount of the solvent component that is necessary for completely stripping the oil solution of the other solvent component or components is dependent on the amount of the latter present in the oil. Since the rainate and extract solutions resulting from the extraction contain relatively large amounts of the solvent mixture, particularly in the case of the extract-solution, we prefer to remove the bulk of the solvent to be stripped by a simple evaporation method prior to the stripping step, in order to reduce the amount of stripping agent required. Moreover, such a preliminary evaporation makes it possible to secure from the oil solution 'the amount of stripping agent needed for the stripping step, both when theA highest or when the lowest boiling solvent component is utilized as previously described.

An object of our invention, therefore, is to provide a method whereby the solvent stripping agent is obtained in sumcient quantity from the solvent mixture utilized in extracting the oil, thus making unnecessary the introduction of an additional amount into the cycle.

In the case of the raffinate-solution the preliminary evaporation may be effected in a single ashstep, the solution being heated and then introduced into an evaporation chamber.

However, in the case of the extract-solution, which contains the bulk of the solvent mixture utilized, it is advantageous to use two, or even three, hash-steps prior to the stripping step.

A feature of our invention resides in the use of two such evaporation stages arranged in series and held under the same elevated pressure, the overhead from the second being used for heating the rst, and the second being heated by steam or other external source of heat. In the rst evaporator the bulk of the low-boiling solvent component will go overhead at a moderate temperature; and the extract-solution which leaves this rst stage can then be heated by steam so as to cause the bulk of the higher-boiling solvent component or components to go overheady in the second stage. Since these higher boiling solvent components can be condensed at a relatively high temperature, their latent heat can be used with advantage for heating in the first stage, and at the same time they will be condensed and thus reduce the amount of solvent vapor to be condensed with cooling water.

By dephlegmating the solvent vapors going overhead in one of the above-mentioned flashsteps, a pured solvent gas can be readily btained for use as the stripping agent.

The hydrocarbon oils to be extracted in a solvent treating plant usually carry a certain amount of water which acccumulatesy in the solvent cycle and will cause corrosion of the equipment if a certain water concentration in the circulating solvent iS surpassed. In order to keep the water concentration of the circulating solvent below the danger point, provision must be made for continuously removing a certain amount of water from the solvent cycle.

According to our invention the overhead vapor, or part of the overheadvapor, from that extract ash-step in which a maximum amount of water is vaporized, is introduced into a fractionation column. 'I'he fractionation, column is operated in such a way that from a certain point pure water, or' at least a liquid solvent-water mixture of atraer@ high water concentration, can be withdrawn. In the latter case, this liquid solvent-water mixture may be further separated by another fractionating step, or simply by settling in case the solvent is'insoluble or only slightly soluble in water.

In the accompanying drawings, wherein we have illustrated our invention, and in which like numerals designate like parts;

Fig. 1 is a ow sheet showing the method of mixed solvent recovery described below in llx ample 1; and

Fig. 2 is a flow sheet showing the alternative method described in Example 2.

Elample 1 This example illustrates a method of recovering and reusing a. solvent mixture consisting of liquid-SO2 and benzol employed for treating a petroleum lubricating oil fraction. In the solvent stripping step, SOz gas is used as the stripping agent, thus illustrating the employment of the lower boiling component of solvent mixtures for this purpose.

The oilto be solvent7treated is pumped into the plant by liquid transfer pump l and forced into the lower part of mixing tower -2 where it rises upwards. In counter-current relation to the oil, the liquid-S02benzol solvent mixture which is introduced into the upper part of the'mixing tower flows downwards through the tower. This solvent mixture comes from the solvent recovery system and is pumped into the mixer by pump 3. On the way to the mixer the solvent mixture passes either through cooler 4 or through heater 5, depending upon the treating temperature desired. i

From the top of mixer 2 the raffinate-solution, that is, the refined oil containing a certain amount of the solvent mixture, flows continuously through a heat exchanger 6 and heater 'I into raffinate condenser-pressure evaporator 8. In this evaporator the major part of the solvent mixture dissolved in the rainate is evaporated l i sure, the raiinate solution ows. over rectifying plates or through layers of filling material downwards, while SO2 gas introduced at the bottom of the column passes upwards through the tower, thus stripping the benzol out ofthe oil. 'Ihe traces of SO2 remaining in the benzol-free railinate leaving the bottom of the stripper are removed in vacuum evaporator I3 with heater I, through which the ramnate flows next. The solvent-free rainate is continuously discharged from vacuum evaporator I3 by means of pump I5 and sent through heat exchanger 6 into storage tanks not show in the drawings. In heat exchanger 6 the hot raffinate is cooled in heat interchange with the incoming raiinate solution which is thus preheated.

The benzol-sulphur dioxide vapors from the stripper l2 are passed through a cooler 3U in which part of these vapors is condensed out under about atmospheric pressure. The condensate is separated from the remaining vapors in trap 3l, and from there it is discharged into collector I0 by means of pump y32. The remaining vapors are passed over to compressor 33 in which they are compressed to a pressure sufliciently high so that they can be liqueed in the water cooled condenser S.

The vapors from the vacuum evaporator I3 are ,first compressed to about atmospheric-pressure by compressor 34 and then further compressed' to condenser-pressure by means ofthe above men-1 tioned compressor 33.

From the base 4of mixer 2 the extract-solution, that is the bulk of the solvent mixture employed for extraction carrying in solution the undesirable constituents removed from the oil, flows continuously through the heat exchanger I6 and through heater I1 into-evaporator I8. In heater I1 the extract-solutionis heated by part of the vapors taken overhead in the evaporator I9, and these vapors are thereby condensed. Evaporator I8 is held at a moderate temperature so that mainly the lower boiling SO2 is removed from the ,extract-solution. Any benzol expelled from the extract-solution with the SO2 is held back by means of liquid-SO2 introduced as a reflux into the top of tower I8. This reflux is supplied from the liquid-SO: collector 21.

From the evaporator I8 the extract-solution flows continuously through steam'heater 20 into evaporator I9 in which, due to the increased temperature, the benzol is largely removed from the extract-solution. The two evaporators I8 and I9 are operated at about the same pressure, and this pressure is slightly higher than that prevailing in the water cooled sulphur dioxide condenser 26 in which the major part of the overhead from evaporator I8 is condensed. The rest of this pure sulphur dioxide-overhead is used for stripping in the strippers I2 and 22. The4 overhead from evaporator I9 is partly used for heatas mentionedabove, and the rest is further processed in fractionating column 28 as described below.

continuously through heater 2I into stripper 22 and from there through heater 24 into the vacuuxn evaporator 23. In these two stages the benzol and sulphur dioxide, respectively, are removed in the same way as in stages I2 and I3 in the raiiinate recovery system, and'are joined with the respective vapors from the latter. The solvent-free extract is continuously withdrawn from vacuum evaporator 23 by means of pump 2.5, Aand forced throughheat exchanger I6 into storage 5o tanks not shown in this drawing. y

p In evaporator I9 a large part of the water entering the extract recovery system with the extract solution goes overhead together with the solvent vapors. In. order to remove this water 55 from the. solvent cycle, part of the overhead from evaporator I9is passed over vinto fractlonating t column 28 in which by means of sulphur dioxidereflux the benzol and thewater are held back -so that an essentially pure sulphur dioxide-over- 60 headleaves the top of the tower.

reboiler.35 provided in the base of the tower by means of which the bottoms, consisting of benzol plus water, are heated up to a temperature sufllciently high so that the sulphur dioxide, is reo8 moved from the benzol-water mixture. The mixture of benzol and water ows from the hase of the fractionator into separator .29 where the water is settled out andlremoved, while the benzol is passed over to collector I0. I

In condenser 9 all mixed solvent vapors-from the recovery system are liquefled and the condensate flows into collector III from which it is4 picked up and forced into mixer 2 by pump 3.

The sulphur dioxide condenser 26 serves for 3 the liquefaction of the sulphur dioxide required ing the incoming extract solution in heater I1 From evaporator I9 the extract solution flows '3|'. and from there'it is passed' over into the 4collector III by means of pump 32'. The non- 'I'here `is a,

for redux in evaporator I8 and in rectier 28. The sulphur dioxide liquefied in this condenser is collected in collector 21 and from there it is -charged to the top vof the towers I8 and 28.

Example 2 This example illustrates an alternative benzol- SOz solvent recovery method and shows the use of benzol vapors as the stripping agent.

The extraction system is the same as that shown in Flg. 1 and described in Example l. Referring to Fig. 2:

The ramnate-solution coming from the top of the mixerflows through heat exchanger 6' and through steam heater 1 into evaporator 8' in which a large part of the mixed solvent is evaporated under condenser pressure. From evaporator 8' the remaining railinate-solution is passed over to the tower stripper 4'0 which is operated at about atmospheric pressure and is equipped with stripping plates'or with filling material. A steamheated reboiler 4I is provided at the base of .tower 49, as part of the stripping system; In this re.- boiler the railinate-solution yafter having passed down through the tower is heated up to such a temperature that the major'part-of the benzol and all the sulphur dioxide is evaporated. The benzol vapors ascending in the tower and coming into intimate contact with the downward flowing raiinate solution exerts a blowing eiect on the raffinate and facilitates the complete removal of the sulphur dioxide. The bottoms leaving this stripping system and containing a certain amount of benzol, are continuously discharged into stripper 42 in which the benzol is stripped out of the oil by means of steam. Pump 43 picks the solvent-free raillnate up from the base of stripper i 42 and forces it through heat exchanger 6' into 'Ihe overhead from the atmospheric stripper 40 passes a water-cooled cooler 30 in which the major part of the benzol is condensed' out from the vapors. The 'condensate is collected in trap condensed vapors are picked up by compressor 33', are compressedto the pressure of the water cooled condenser 9 and discharged into the latter.

The overhead from stripper 4.2, consisting of benzol and water vapor, is passed through the watercooled cooler in which the total vapors 1 are liquefied. In the separator 6I the water is settled out from the benzol and removed from the solvent cycle, while the benzol is passed over into trap 3l* where it is combined with the condensate from cooler 30', and from where it is recycled,l into the solvent collectorIU' by pump 32'.

The extract-solution coming from the base ofythe' mixer flows through heat exchanger I6' and vthrough heater I1 into evaporator 46. In heatexchanger I6' the cold extract-solution is preheated by heat interchange with the hot solvent-free extract, while in heater lI1 further heating of the extract solution is done by means of solvent vapors coming from vevaporator I9' and being condensed in this heater. The temperaoov ture maintained in evaporator 46 isrelatively low is taken overhead in this evaporator. This over-n head is combined with the solvent vapors coming from rainnate evaporator d', and the total mixed solvent vapors are passed over to the water cooled condenser 9' where they are liqueed. The condensate nows into solvent collector it and from there back into the mixer as shown in Fig. l.

The extract solution leaving the base of evaporator 56 cws continuously through steam heater 20 into evaporator I9. Due to the increase in temperature a large amount of the benzol originally present in the extract soiution is removed in this evaporator together with sulphur dioxide. Part of the overhead from the evaporator is used for preheating the incoming extract solution in heater l1' as described above, While the remainder" of the vapors leaving this evaporator is passed over into the fractionator 28 for further proc- 'essing as described below. The solvent condensate from heater I1' iiows into the mixed solvent collector iil.

From evaporator lil' the extract-solution iows to stripping tower 59, provided with reboiler 50, and from there to stripper 5i. These two stages are operated in the same way as .strippers dii and 32, respectively, on the raiinate side. Pump 25' discharges the solvent-free extract from stripper di and pumps it through the above mentioned heat exchanger i6 into storage tanks not shown in the drawings. The overheads from strippers $9 and 5i are respectively combined with those from strippers it and t2, and the succeeding steps with respect thereto are as described above in connection with the latter.

The removal of the water from the stream of extract solution is in this plant done in the following way. The solvent vapors going overhead in evaporator. i9 will carry a relatively large amount of water since here the bulk of the benzol is evaporated, the boiling point of which is nearer to that of the Water than that of the sulphur dioxide. As in Example 1, part of this overhead is passed over into the tower fractionator 2B'. In this case the Water and the benzol are held back by means of the dephlegmator cooler 54 provided on top of the fractionator, so as to secure a dry SO2 overhead. In the base of fractionator tower 28.the mixture of benzol, sulphur dioxide and water is reboiled whereby the sulphur dioxide is removed from the mixture. In separator 29' the water is settled out from the benzol and re- Vmoved from the cycle, While the benzol is transferred to the reboiler 50 in order to increase the stripping effect for the removal of the sulphur dioxide in tower 49,

In the claims it will be understood that the term oil fraction embraces both raflinates and extracts, since theseare obtained by solvent fractionation; 'Ihe term solvent aid includes one or more components. The term condenser-pressure for SO2 means apressure such that SO2 vapor `evolved under this pressure can be passed to a water-cooled condenserQ and there liquefied without pumping or other means for increasing its pressure being required. v

It is obvious that the process may be applied to the recovery of solvents used for deasphaltizing,

, dewaxing, and other modes of treatment of lubri- 'eating oil fractions utilizing mixed solvents.

Having disclosed several embodiments of the invention fory purposes of illustration, but Without any intent to be limited thereby either as to the particular steps or combinations of steps described, what we claim is as follows:

l. In a process of treating a mineral lubri-A atesora eating oil with a plurality of lower-boiling solvents, the method of recovering a mixture oi solvents contained in an oil fraction, after said treatment, which comprises removing the bulk of the solvent mixture by simple evaporation, subsequently stripping the oil fraction with the vapor of a solvent which has been utilized in the treatment and later separated out, at a pressure and temperature to remove the other remaining solvent material, removing the residual solvent to complete the removal of the treatment solvents, and collecting the removed solvents in condition for reuse.

2. In a process of treating a mineral lubricating oil with a plurality of lower-boiling solvents, the method of recovering a mixture of solvents contained in an oil fraction, after said treatment, which comprises removing the bulk of the solvent mixture by simple evaporation, subsequently stripping the oil fraction with the vapor of a solvent Which has been utilized in the treatment and later separated out, at a pressure and temperature to remove the other remaining solvent material, removing the residual solvent to complete the removal of the treatment solvents by 4subsequently stripping the oil fraction With a gaseous agent readily removable therefrom and from the evolved solvent, and collecting the removed solvents in condition forA reuse.

3. In a process of treating a mineral lubricating oil with a plurality of lower-boiling solvents, the method of recovering a mixture of solvents contained in an oil fraction, after said treatment, which comprises removing the bulk of the solvent mixture by simple evaportion, subsequently stripping the oil fraction with the vapor of a solvent which has been utilized in the treatment and later separated out, at a pressure and temperature to remove the other remaining solvent material, removing the residual solvent to complete the removal of the treatment solvents by subsequently subjecting the oil fraction to evapora` tion at a suitable temperature and pressure,and collecting the removed solvents in condition for reuse. v

4. In a process of treating a mineral lubricating oil with a lower-boiling selective mixed-solvent containing liquid-SO2, the method of recovering the mixture of solvents contained in an oil fraction, after said treatment, which comprises removing the bulk of the solvent mixture by simple evaporation, subsequently stripping the oil fraction with the vapor of a solvent which has been utilized in the treatment and later separated out, at a pressure and temperature to remove the other remaining solvent material, removing the residual solvent to complete the removal of the treatment solvents, and collecting the removed solvents in condition for reuse.

5. In a process of treating a mineral lubricating oil with a selective solvent mixture of liquid- SOn and benzol, the method of recovering the liquid-SO2 and benzol contained in an oil fraction, after said treatment, which comprises removing the bulk of the solvent mixture by simple evaporation, subsequently stripping the oil fraction with the vapor of one of the named solvents which has been utilized in the treatment and later separated out, at a, pressure and temperature solventV aid of lower boiling point than the oil ing oil with a selective solvent mixture of liquid- SOz and benzol, the method of recovering the liquid-SO2 and benzol contained in an oil fraction, after said treatment, which comprises removing the bulk of the liquid-SO2 and benzol by simple evaporation, subsequently stripping the oil fraction with the'vapor of SO2 which has been utilized in the treatment and later separated out,

at a pressure and temperature to remove the remaining benzol, removing the residual SO2 by v vaporization, and collecting and condensing the removed SO2 and benzol vapors in condition for reuse.

'7. In a process of treating a mineral lubricating oil with a selective solvent mixture of liquid- SO2 and benzol, the method of recovering the liquid-SO2 and benzol contained in an oil fraction, after said treatment, which comprises removing the bulk of the liquid-SO2 and benzol by simple evaporation, subsequently stripping the oil fraction with the vapor of SO2 which has been utilized in the treatment and later separated out,

at a pressure and temperature to remove the remaining benzol, removing the residual SO2 by subjecting the oil fraction to evaporation under vacuum, and collecting and condensing the removed SO2 and benzol vapors in condition for reuse.

8. In a process of treating a mineral lubricating oil with a selective solvent mixture of liquid- SOz and benzol, 'the method of recovering the liquid-SO2 and benzol contained in an oil fraction, after said treatment, which comprises removing the bulk of the liquid-SO2 and benzol by simple evaporation, subsequently stripping the oil fraction with the vapor of benzol which has been utilized in the treatment and later separated out, at a pressure and temperature -to'remove the remaining SO2, removing the residual benzol by vaporization, and collecting and condensing the removed SO2 and benzol vapors in condition for reuse` 9. In a process of treating a mineral -lubricating oil with a selective solvent mixture of liquid- SO2 and benzol, the method of recovering the liquid-SO2 and benzol contained in an oil fraction, after said treatment, which comprises removing the bulk of the liquid-SO2 and benzol by simple evaporation, subsequently stripping the oil fraction with the vapor of benzol which has been utilized in the'treatment and later separated out, at a pressure and temperature to remove the remaining SO2, removing the residual benzol by stripping with steam and removing the steam from the evolved benzol, and collecting .and condensing the removed SO2 and benzol vapors in condition for reuse.

10. A method of recovering from a mineral lubricating oil fraction a lower-boiling solvent mixture contained thereinj following solvent treatment of the oil, the solvent mixture including l .several components of substantially different boiling points, which comprises vaporizing the bulk of the lowest boiling solvent component by heating theoil fraction at least partially with higher boiling vapors derived ina subsequent step, subsequently heatingthe oil to a higher temperature to vaporize the bulk of the remaining solvent and provide said higher boiling vapors, stripping ricating oil fraction a selective solvent mixture o f liquid-SO2 and a'substantially higher-boiling contained therein following solvent treatment of the oil, which comprises vaporizing the bulk of the liquid-SO2 by heating the oil fraction at least partially with higher boiling vapors of the solvent aid derived in a subsequent step, subsequently heating the oil toa higher temperature to vaporize the bulk of the remaining solvent aid and provide said higher boiling vapors, stripping the oil fraction with a constituent of said solvent mixture, completing the removal of the solvent mixture from the oil fraction, and collecting the removed solvents in condition for reuse.

12. A method of recovering from a mineral lubricating oil extract-solution a solvent mixture of liquid-SO2 and benzol contained therein, which comprises subjectingthe extract-solution to evaporation in two stages under condenser-pressure for SO2, heating the extract-solution in the iirst stage with benzol vapors derived from the second stage so as to vaporize the bulk of the liquid-SO2, heating the extract-solution from the rst stage at a higher temperature in the second stage to vaporize the bulk of the benzol, thereafter stripping the extract-solution withone component of the solvent mixture to remove the balance of the other, completing the removal of the solvent mixture, and collecting theremov'ed solvent mixture in condition for reuse. I

'13 a A method of recovering from a moisturecontaining mineral lubricating oil extract-solution a solvent mixture of liquid-SO2 and benzol contained therein, which comprises subjecting the extract-solution to evaporation in two stages under condenser-pressure for SO2, heating the extract-solution in the first stage with benzol vapors derived from the second stage Vso as to vaporize the bulk of the' liquid-SO2, heating the` ricatingoil extract-solution a solvent mixture of liquid-SO2 and benzol contained therein, which comprises subjecting the extract-solution to evaporation in two stages under condenser-pressure for SO2, heating the extract-solution inA the first stage with benzol vapors derived from the second stage so as tovaporize the bulk of the liquid-SO2, heating the extract-solution from the rst stage at a highertemperature in the second stage to vaporize the bulk of the benzol, purifying a portion of the benzol vaporlzed in the -second stage and stripping the extract-solution from the second stage therewith, completing the removal of the solvent mixture, and collecting the removed s01- vent mixture in condition for reuse. 15. A method of recovering from a numeral lubricating oil extract-solution a solventmixture of liquid-SO2 and benzol contained therein, lwhich comprises subjecting the extract-solution to evaporation in two stages under condenser-pressure for SO2, heating the extract-solution in the iirstf stage with benzol vapors derived from the vsecond stage so as to vaporize the bulk of the liquid-SO2, heating the extract-solution from the rst stage at a higher temperature inA the second stage to vaporize the bulk of the benzol, dephlegmating the SO2 vaporized in the iirst stage and stripping the extract-solution from the second stage therewith, completing the removal of the solvent mixture, and collecting he removed solvent mixture in condition for reuse.

16. In a process of solvent-refining lubricating oil stock with liquid-SO2 and benzol, the method of recovering the liquid-SO2 and benzol contained in the extract-solution which comprises subjecting the extract-solution to evaporation in two stages under condenser-pressure for SO2, heating the extract-solution in the first stage with benzol vapors derived from the second stage so as to vaporize the bulk of the liquid-SO2 and condense said benzol vapors, heating the extractsolution from the iirst stage at a higher temperature in the second stage to vaporize benzol for use in the rst stage as above-specified; dephlegmating the vapors derived-from said first stage, and any vapors derived from said second stage not employed for heating the first stage, to secure benzol-free SO2 vapor; stripping at atmospheric pressure the extract-solution from said second stage with said benzol-free SO2 vapor to free the same of benzol; subjecting the stripped extract- Solution to evaporation under vacuum to remove the SO2 contained therein, thereby securing solvent-free extract; and condensing and collecting the evolved SO2 and benzol vapors for reuse in refining oil stock.

17. In a process of solvent-refining lubricating oil stock with liquid-SO2 and benzol, resulting in a raffinate-solution and an extract-solution, including the securing of benzol-free SO2 vapor from the extract-solution, the steps of recovering the liquid-SO2 and benzol contained in the rainate-solution which comprise heating the raffinate-solution under condenser-pressure for SO2 to evaporate the bulk of the liquid-SO2 and benzol contained therein, stripping the raflnate-solution at atmospheric pressure with said benzolfree SO2 vapor from the extract-solution to remove the remaining benzol contained therein, subjecting the stripped rainate-solution to evaporation under vacuum to remove the SO2 contained therein, thereby securing solvent-free raffinate, and condensing and collecting the evolved SO2 and benzol vapors for reuse in refining oil stock.

18. The method of refining mineral oil which comprises extracting it with a mixture of high boiling and low boiling solvents, separating the oil contaminated by solvents from the solvent containing the extract, and separately recover- -ing solvents from each fraction by vaporizing most of the high boiling solvent from the oil and stripping the remainder of the high boiling solvent therefrom by introducing vaporized low boiling solvent at a low point to contact directly with the high boiling solvent and oil.

19. In a system of the type described, means for extracting oil with a mixture of a high boiling and a low boiling solvent, means for heating the extracted oil contaminated with said solvents to a temperature at which substantially all of said solvents are vaporized, means for rectifying the vapors to effectively fractionate the low boiling and high boiling solvents and. to separate the high boiling solvent from the oil, and means for introducing vaporized 10W boiling solvent in the oil solvent separating means withdrawn from another point in the system at a low point in the oil solvent separating means to contact directly with the high boiling solvent and oil for removing the last traces of high boiling solvent from the oil.

20. A method of rening petroleum oil which' comprises separating naphthenic from parailinic constituents of the oil with a solvent mixture in which the solvents have a boiling point lower than that of the oil and at least one solvent has a boiling point lower than any other solvent, separately heating the naphthenic and paramnic fractions to temperatures sufficient to vaporize most ofthe solvent mixture contained therein, vaporizing the mixed solvents from the heated oil, rectifying the vapors to remove oil from the solvents, and introducing a portion of the lower boiling solvent into the non-vaporized oil at a temperature sumcient to produce the complete vaporization of said lower boiling solvent whereby it serves as a stripping gas to remove the last traces of solvent from the oil.

21. An oil rening process which comprises separating parainnic from naphthenic constituents of a petroleum oil by extracting said oil with a mixture of a high boiling and a low boiling solvent, both of said solvents and the solvent mixture having a boiling point below that of the oil, separately heating the parailinic and naphthenic fractions to a temperature sumcient to cause vaporization of both solvents, separating the vaporized solvents from unvaporized oil contaminated with solvents, rectifying the vaporized solvents to remove oil therefrom, introducing condensed low boiling solvent for use as a reux liquid in said rectifying step, and introducing a portion of said low boiling solvent into said unvaporized oil at a temperature high enough to cause complete vaporization of said low boiling solvent whereby it serves as a stripping means for removing the remaining high boiling solvent from the unvaporized oil.

, 22. The method of refining mineral oil which Icomprises extracting it with a solvent mixture for separating paranic from naphthenic fractions, said solvent mixture comprising a high boiling and a low boiling solvent, separating the paraiinc oil fraction from the `naphthenic oil fraction, each of which being contaminated with solvents, vaporizing most of the solvents from each fraction and stripping the remaining high boiling solvent from the oil by introducing vaporized low boiling solvent at a low point to Contact directly with the high boiling solvent and oil whereby the high boiling solvent is stripped from the oil with low boiling solvent so that the system is not contaminated With extraneous stripping gases.

23. The method of claim 20 wherein the low boiling solvent is superheated prior to its use as a stripping agent.

24. The method of claim 21 wherein the low boiling solvent is superheated prior to its use as a stripping agent.

25. In apparatus for rening of petroleum oils by use of a mixture of solvents comprising a high boiling solvent and a low boiling solvent, which includes mixing and settling equipment for commingling the oil with the solvent mixture and obtaining a separation thereof into rainate and extract portions, means for separately treating said portions comprising an evaporator for driving ofi the low boiling solvent by moderate heating, a gas and liquid separator having a vapor outlet at its top for separating the high boiling solvent from the oil, said separator having an inlet near its bottom for admitting vaporized low boiling solvent for stripping out the high boiling lsolvent in vapor form, means for circulating the vaporized solvents including a compressor and andere 7 heating the hydrocarbon oil containing sulphur dioxide and benzene in solution, stripping said heated oil in countercurrent contact with heated sulphur dioxide vapors and producing thereby overhead vaporsv of sulphur dioxide and benzene and a bottom hydrocarbon oil substantially free 5 from benzene.

ERNST KOENEMANN. HANS RAMSER. 

